Acylated hydroxylated polyamine



' -Patented May 8, 1945 I UNITED STATES PATENT orrlcs r 2,375,532ACYLATED HYDROXYLATED POLYAMINE Melvin De Groote, University City, andBernhard Keiser, Webster Groves, Mo., Petrolite Corporation, Ltd.,Wilmington, corporation of Delaware assi'gnors to Del., a

N Drawing. Original application September 8, 1941, Serial No. 410,086.-Divided and this application June 26, 1943, Serial No. 492,650

1 12 Claims. (01. 260-4045) Although one of theqprimary objects of ourinvention is to provide a new compound or composition of matter thatisan. efflcient demulsiher for crude oilemulsionsofthe .water-in-oiltype, the said compound or composition of matter is adapted for use inother arts, as hereinafter indicated. i I

The new chemical compound or composition of matter herein describedgisexemplified by the acidic; or preferably, neutralester derived bycomplete esterification of one mole of a polyalkylene glycol of the kindhereinafter described, with two moles of 'a'fractional ester derivedfrom a hydroxylated material of the kind herein described, and apolybasic carboxy acid having not over six carbon atoms.

If a hydroxylated material, indicated for the sake of convenience, bythe formula T.OH, is reacted with a p'olybasic carboxy acid,. which,similarly, may conveniently be or the dibasic type and indicated by theformula HOOC.D.COOH- then the fractional ester obtained by reactionbetween equimolar quantities may be indicated by the following formula:

I- IOOC.D.COO.T

omozmo mn in whichjm varies from .7 through 17.

Instead ofpolyethylene glycols,one' may use polyproylene glycols. or"polybutylene glycols. Thus, for convenience, in the broadest aspect,

the polyalkylene glycols employed may be indicated by the followingformula:

omcnnzno) me in which m hasits previous significance, and :n representsa numeral'varyingfrom 2 to 4.

Thus, the bulk of the materials herein contemplated, particularly for usas demulsifiers, may be indicated within certain variations, ashereinafter stated, by the neutral esteraderived by esterification ofone mole of a glycol of the kind above described, with two moles of atrap tional ester of the. kind previously described. The formation ofthe compound may be indi cated by the following reaction, althoughobviously, it is immaterial what particular procedure is employed toproduce theparticular chemical compound or product: I

.rooonooona oncozrno)mH+Hooo.D.ooo.T T.OOC.D.COO(C2H4O) m l'ozmoooncoogr1 As indicated previously, the polybasic acids employed are limited-tothe type having not largely, with convenience of manufacture of thefinished ester, and also of the price of the re acta'nts. Generallyspeaking, the higher the temperature employed, thev easier it is toobtain large yields of the esterified product. Although oxalic acid iscomparatively cheap, it decomposes somewhat readily at slightly above;the boiling pointof water. For this reason, it is more desirable tousean'acid which ismore resistant to pyrolysis. Similarly, vwhen.a'polybasic acid 'is available .in the form of an anhydride, suchanhydride is apt to produce: the ester with greater. ease than the aciditself. For this reason, maleic anhydride is particularly adaptable;also, everything else considered, the

' .cost is comparativelylow on aper molar basis, even though somewhathigher on-a per pound basis. Succinic acid or the anhydridehas many ofthe attractive qualities of amaleic anhydride; and this is also true ofadipic acid; For purposes of-brevity, the bulk of the compoundshereinafter disclosed will refer to the =use..;of

maleic anhydride, although it is understoodthat any other suitable.polybasicacid may; be

' employed. Furthermora for purposes of conethylene glycols.

ethylated compounds is due, largely, to the fact that they arecommercially available; and par-- erence to employ those havingapproximately 812 oxyalkylene groups, particularly 8-12 oxy ethylenegroups. Our preference to-usetheoxyticularly so in two desirablefblrmsrThemos-t1 desirable. form is the so-ca'lledmonaethylene' gly col, which,although consisting largely of nonaethylene glycol, may containwsmall:amounts of heptaethylene. and octaethylenei Ely-001$. .and

possibly minor percentages of the higher lionio logues. Such glycolsrepresent the upper range of distillable glycols; and they maybeconveniently referred to as -upperdistil1able= ethyl- 1 one glycols.Thereis noiparticularly goodLprocedure for makingga sharper separationon a commercial scale; and it is understood that mix- "tures of oneorsmore of' the glycols may be employed, as well as-asingleglycol'.Aspointed' out,

' it is particularly preferred to employnonaethylene glycol ascommercially available, although: it

is understood that this: product contains other homologues, asindicated.

Substantially as desirable as the upper distillabl'e polyethyleneglycols are the lower nondistillable polyethylene glycols. I r areavailable in the form ofa waxy water-soluble material, and the generalrange may vary somet what from d'ecato te'tradecaethylene glycol;

a fractional acidic ester, then if .two molesof the fractional acidicester are reacted with one mole of the polyethylene glycol, there is nopossibility for the formation of polymeric types of esterificationproductsunder ordinary conditions. 1

The alcoholicbodies-employed as reactants'in one mode of manufacture ofthe present compounds are basic hydroxylated polyacylated polycarboxyacid, preferably non-hydroxy in nature,

having not more than 5 carbon atoms and linked to the twoterminalnitrogen atomsj (bl An acyl radical derived from a detergentforiningmonocarboxy acid having at least 8 and not more: than. 32. carbon atoms;and

' (c)= alcoholiform' hydroxyl radical.

The preferred form'of alcoholic body is characterized by not only thethree above enumerated characteristics, but also the additionalcharacteristic of? having present 'a basicamino hydrogen group, i. e.,.an; amino hydrogen radical free. from directly linked acyl radicals or:aryl radicals. Furthermore, this preferred type: of. alcoholic body, aswell as the modification having no hydroxyligroup s, is: effective as a:demulsifier per se under thegsame conditions and when used in: the samemanner as the demulsifier. herein contemplated. far as we are aware,suchtype of-material', subsequently described in. greater detail,

' is a new composition of' matterwper' se.

These materials 7 is well understood, the method of producing suchglycols would cause some higher homologues to be formed; and thus, evenin this-instance, there may bepresent some oxyethylene glycol's withinthe higher range above indicated; One need not point out that theseparticular compounds consist'of'mixtures, and that in some instances;particularly desirable esters areobtained by making 6 mixtures of theliquid nonaethylene glycol with the soft, waxy,'lowernon-distillablepolyethylene 'glycols.

For the sake of' convenience, reference mane examples wi-ll be to:nonaefliylene'glycol;

and calculations will'be based on a theoretical molecular weight of414-. Actually, "in manufacture, the molecular weight of. the glycol:employed,

a mixture of the same, should be determined and reaction conductedonthebasi's of such determination, particularlyin coniun'cti'onwith thehy- .col or mixtures of glycols with maleic'anhyd'ri'de ina ratio of twomoles oi' the anhydride for one mole'of the glycol. Undersuchcircumstances,

we have-found little tendency" to form'jlonger whether a higherdi'stillable polyethylene glycol or alower non-'di'stillablepolyethylene glycol; or

Attention is. directed to our two co-pendi'ng ap plications for patentSerial Nos. 401,378 and 401,381, both filed July 7, 1941, which: maturedas U. SL-Eat'ents Nos. 2,324,490 and 2,324,493, respectively, bothdatediJuly 20, 1943; I,

Asexamples of reactants employed in the manufacture of the. alcoholic:bodies herein. contemplated, particularly as intermediates, there areincluded, among: others, diethylene-triamine, 'triethylenetetramine,tetraethylenepentamine, and. comparable derivativesiderived from propylenedichloride; butyl. dichloride, amylene dichlo ride, and the like.'Indeed', instead of using propylene: dichloride as a. reactant forproducing a 'satisfactorypolyamine for use as a rawmaterial, one: canemploy the comparable amine derived from glycerol dichlorhyldrin, i.e.,v betahysoap or soap-like bodies. The detergent-forming acids,inturn,.- in clude naturally-occurring fatty.

acids, resin acids-such asabietic acid, naturallyoccurring petroleumacids, such as naphthenic acids, carboxy acids produced by the oxidationchain polymers; and in fact', theproduct of reaction, if conducted" atffreasonably low temperatures; appearswto be'largely'monoineric. Forconvenience, such intermediate fractionai ester may then'be consideredas ajdibasi-cor'polybasic acid. One mole of the intermediate-fractionalester, so obtained, is then reacted with two' moles of'the alcoholicmaterial of the kind subsequently described. I

It isto be=noted, however, that-itone prepares of petroleum, .etc.-

As to oxidized petroleumacids, see U. S. Patent No. 2,242,837, dated May20, 1941', to Shields.

As is well known, there are other acids having a similar characteristicsand derived from a somewhat different, source and difierent instructure, but which can be included within the broad generic'termpreviously indicated. Such acids have at least 8 carbon atoms and notmore than32 carbon atoms, and the most desirable form isex emplified bythe fatty acids, particularly the unsaturated fatty acid.

less are exemplifiedbyfacetic acid, formic acid, propionic acid, butyricacid, furoic acid, lactic acid, hydroxybutyri'c acid, etc.; however, thenonhydroxylated type are most desirable, i. e., the

acids, more especially by ricinoleic Thelow molal acids having 5 carbonatoms or i type other than lactic acid, hydroxybutyric.v acid, etc Anumber of suitable amines have already been suggested. Y Reference ismade to U. S. Patent No, 2,243,329, dated May 27, 1941,to De Groote andBlair. This patent lists a large number of polyamines containing threeor more basic amino groups.

' offtwo moles of ethylene oxide produces two hy- It also includesdescription of procedure 'generally employed for acylation by means of ahigh molal or low molalacid. It is understooiof course, that one neednot employ the acid itself, but the acid radical may beintroduced byemploying an ester, anhydride, amide, acyl chloride, or any othersuitable form. I

The following examples will serveto illustrate I:

the manufacture of such acylated polyaminolcompounds. It is to be notedthat in many instances it is most convenient to first introducean acylradical of a low molal carboxy acid of the kind described, and thenintroduce-the acyl radical from a high molal carboxy acid of the kinddescribed. The introduction of the high molal acyl radical may be in anamido form, or in an ester form. In some instances, this may, requirethe treatment of the first acylation product with ethylene oxide or thelike. All of this is obvious to the skilled chemist, in View of Whathasbeen said; but the following examples will illustrate the matter evenfurther:

INTERMEDIATE ACYLATION PRODUCT Example 1 One pound mole of diethylenetriamine is treated with 2 pound moles of methyl acetate so as'to give adiacetylated product of the type characterized by the fact that the twoacetyl radicals are attached to the terminal nitrogen atoms, the reasonbeing that the primary amino radical acylates more readily than thesecondary amino radical.

INTERMEDIATE ACYLATION PRODUCT 7 Example 2 One pound mole of theproductof the kind described under Example 1, preceding, is treated with onepound mole of ethylene oxide, so as to give the hydroxyethyl derivative,which may be indicated in the following manner:

C2H40H INTERMEDIATE AcYLATIoN PRO UCT Example The same procedure isfollowed as in Example 2, except that 2 poundmoles of ethylene oxide areused, thus introducing a hydroxylated radical containing an etherlinkage. In other words, the secondary amino hydrogen atom is replacedby the group C2H4OC2H4OI-l. lhe compounds so obtained may be indicatedinthe followingv manner:

. /NC2H4NCzH-\N H 0Com (EH40 C2H|OH INTERMEDIATE ACYLATION PRODUCTExample 4 CHsCO Triethylene tetramine is substituted fordiethylenetriamine in the Intermediate acylation product, Examples 1, 2and 3, preceding. 7 It is to ethylene oxide must be employed,

droxyethyl groups in the oxyethylated product; andin order tointroducethegroup one .must employ at least 3 moles ,of ethylene oxide.v I

INTERMEDIATE ACYLA'IION PRODUCT Eaample 5 The-same procedure is followedas in Example 4, except that tetraethylenepentamine is'gsubstituted fortriethylenetetramine. In this instance,

in order to obtain a hydroxylated radical containing the ether-linkage,at least 4 molesof INTERMEDIATE ACYLATION P O CT Example 6 Productscomparable to Examples 1e5,,preced ing, are obtained from polyamines,which, in

turn, instead of being, derivatives of ethylene dichloride, arederivatives of propylenedichloride;

INTERME IATE ACYLATIoN PRODUCT 1' Example 7 Polyamines derived fromglycerol dichlorhydrin I (betahydroxypropylene dichloride) p t H OHClCO'C-C1 ,B I aresubstituted for the' amines employed inthe preceding.example,.. i. e., propylene dichloride.

COMPLETELY .ACYLATED PR'oDucTs I Examplel One pound mole 'of theproductsof the kind. described in Intermediate acylation products, Ex- I 'amples2-7, inclusive, are treated with one pound mole of oleic acid, so astoproduce a polyamino amide of' the kind previously described.

for oleic acid in in aforementioned Shields Patent'No. 2,242,837,having, approximately 12-16carbon atoms and i being ofthe branch chaintype, are substituted for oleic acid in the previous example. I

C MPLETELY ACYLATED PRODUcTs Example 6 In some instances, Wherederivedfromtetraamine or penta-amino compounds, it is possible tointroduce more than one high molal acyl group,

For instance, one might introduce two ricinoleyl radicals, or onericinoleyl radical and oneoleyl radical.

be noted in this instance, however, that the i'ise.

amines l derived from' lltthasjbeen previously pointed outthatrthe Yalcoholic bodies herein contemplated .for reaction with.nonaethyleneglycol dihydrogen dima-leate nonethylene. glycol dihydrogen;di-ma;leate,; if .de-i

or the equivalentdibasiafractional ester, represent, in part,a sub-genusof a broader class, and that this broader classification per serepresents valuable demulsifying agents withoutfurther re:

1 action;

The alcoholic. bodies'herein employed. as react ants need not have abasic amino nitrogen atom;

and obviously, do not have, when derived from a reactant suchasdiethylene-triamine ln'certain instances. For[example, if one poundmole of diethylene triamine is reacted with'2 pound moles of aceticacidor its equivalent, one obtains. the" diacetylated product. Ifsuchproduct is then acylated,-for example, with-ricinoleic acid, the,

' body for reaction with nonaethylene glycol di-- sired. .I-Ioweverpinthis, type of material, i., -.e-.- where there is present 2 terminal.acyl radicals derived: from a low molal ,carboxy acid;- and: I

where there is present-at least 2: basic amino nitrogen atoms, and atleast one high molal acyl radical, one has an, efiective 'demrulsifieiz-If hydroxylated, it may serveas an alcoholic hydrogen dimaleateg.and1alcoholic bodies of a similar type containing no basic-amino groupswill alsoserve-as reactants for combinationFwith nonaethylene glycoldihydrogen dimaleateor the like.

As specific examples ofithe-types of compounds which may be. employed asdemulsifiers for water- I 1 on-oil emulsions, without reactionwithnonaresultantv product is hydroxylated, but is not .basic incharacter, insofar that there is not present an amino nitrogen atom freefrom link-' age with an aryl radical or acyl radical. It is well'knownthat linkage; of. an. aminonitro'gen' atomwith an acyl radical, orwithan aryl radi-f caLenOrmousIyreduces or substantially eliminatesbasicity.

If, 'howcver, such diacetylated diethylenetri amine is treated with-onemole of ethylene oxide 7 andif such product is then treated withricinoleic acid, the acyl radical, orfmore specifically, the ricinoleylradical, enters as part of an ester link-j age and not an .amidolinkage.

and is also basic in character, 1. e., a valuable demulsifier as is,WithOlltfllI'thGlflGaCtiOIl, Fur-j thermore, if the same oxyethylatedproduct is treated with oleic acid, the resultant compound is alsoa'valuable demulsifier, but, is ofno value for'manufacturing thefinalcomposition of mat 'ter herein contemplatedfior the reason that there iis no residual hydroxyl radical ,to permit com-j bination withnonaethylene glycol dihydrogen'di maleate, or thelike; F

Such product exemplifies a type which is an alcoholic body,

' From apractical standpoint, the manufacture of the reagents which arevaluable demulsifying ag'ents, although not alcoholic bodies,- hasalready been suggested. This is obvious by referring back toIntermediate acylation products, Exf amples 4 and 5, wherein there aredirections for treating triethylenetetramine and tetraethylene-gpentaminewith 2 moles, of acetic acid, methyl ,acetate Or the like, soas to convert the primary amino groups into'the diacetylatedderivatives.

Since there still remain 2 or 3 basic amino nitrogen atoms, one canacylate with a high-molal acid, such as oleic acid, ricinoleic acid, orthe like, in

.boXy acids, which mayor may not be hydroxyfact, mightintroduce two suchacids in the in stance where the derivative is obtained fromtetraethylenepentamine.

intermediate would serve as an alcoholic body; but if derived from oleicacid, abietic acid; naphthenic acid, or'the like-,this would not betrue. However, such product would serve as a demulsifier without furtherreaction with 'nonae'thylene glycol,- or the like. Similarly, regardlessof whether the high molal, acyl group introduced contained a hydroxylradical or not, i. e., even in such instances Where. the product isderived from oleic acid, naphthenicacid, or the like, the reactionproduct can be'treated further with ethylene oxide, propylene oxide, orthe like, I so as to introduce a hydroxyethyl .or an l oncznroczrn gradical, and thus permit subsequent reaction with If derived from a by'droxylatedacid, such as ricinoleic acid, then the ethyleneglycoldihydrogen dimaleate, attention 7 Structural formulaC II t ll IRCNCZHlbfCflHlNCBH lNiC R H(|3H RC H O O CR 7 Structural formulaD R'COrepresents acyl radicals of low'molal" carboxy acids, and RCO, radicalsof high molal carlated, i. e., may-represent oleic acid or ricinoleicacid. I In each instance the arrow points to the basic amino group.

Comparable products may be derived from tetraethyleneepentamine in whichthe. same basic type of radical appears, or a combinationof basic types.It is to be noted that the efilcient method of producing the compoundshereincontemplated is by first treating the selected primary rawmaterial with acetic acid orthelike, so as to intro duce the terminalacetyl radicals, the reasonjbeing that such reactions are readilycontrollable. soas to enter the terminal position, since the terminalamino groupings are primary aminogroups and acylate more rapidly andmore completely than the internal amino groups which are 'sec-.

ondary amino radicals. In compounds of the kind just described, it is tobeemphasiz ed once morejthatall these represent valuable demulsi- 'fiersas is, and as far ,as we are aware, new compositions of matter per se.

Where 'hydroxylated, whether it be due to the, presence of a hydroxy- 9ethyl group, a ricinoleylfgroup, or the like, such next step, of course,is to obtainfractional esters derived from nonaethyle'ne glycol ofthekindde scribed in the earlier part of the present disclosure. Suchmaterials may be'ill'ustrated by the'followingz V GLYcoL ESTERINTERMEDIATE PRODUCT Example 1 7 One pound mole of nonaethylene glycolis re acted with two pound moles of maleic anhydride, so asto formnonaethylene glycol dihydrogen dimaleate. 1

GLYcoL ESTER INTERMEDIATE PRODUCT Example 2 A mixture oflowernon-distillablepolyethylene glycols, representing approximatelydecato tetradecaethylene glycol, is substituted fornonaethylene glycolin the preceding example.

GLxooL ESTER INTERMEDIATE PRODUCT Examplet H a f A 50-50 mixture ofnonaethylene glycol and lower non-distillable polyethylene glycolsof thekind described in the previous example is substituted for nonaethyleneglycol in Example 1. I

Citric acid is substituted for maleic anhydride in Examples 1-3,preceding.

' GLYCOL ESTER INTERME IATE, PRonocT Example 7 Succinic anhydride issubstituted for maleic anhydride in Examples 1-3, preceding.

The method of producing such fractional esters is well known. Thegeneral procedure is to employ a temperature above the boiling point ofwater and below the pyrolytic pointfof the reactants. The products aremixedand stirred constantly during the heating and esterification step.If desired, an inert gas, such as dried nitrogen, or dried carbondioxide, may be passed through the mixture. Sometimes it is desirable toadd an esterification catalyst, such as suliuric acid, benzene sulfonicacid, or the like. This is the same general procedure as employed in themanufacture offethylene glycol dihydrogen diphthalate. SeeU. S. PatentNo. 2,075,107, dated March 30, 193'7,to Frasierj j ,1 1 1 Sometimesesterifica-tion is conducted most readily in the presence of aninert'solvent, that carries away thewater of esterification which may beformed, although, as is readily appreciated, such water ofesterification is absent when the 5 reaction involves an acid anhydride,such as maleic anhydride, and a lycol. However, if water is formed, forinstance, when citric acid is employed, then a; solvent such as xylenemay be present andemployed to carry off the water formed.

The mixture of xylene vapors and water vapors can be condensed so thatthe water is separated. The xylene is then returned to the reactionvessel for further circulation; This is a conventional and well knownprocedure and requires no further elaboration.

COMPOSITION OF MATTER Example 1' Two pound moles of a, hydroxylatedmaterial of the kind exemplified by fCompletely acylated products,Example 1 are reacted with one pound mole of a glycol ester intermediateproduct of the kind described under Glycol ester intermediate products,Examples 1, 2 and 3, preceding. Such reaction is conducted untilsubstantially all carboxyl acidity has, disappeared. The time ofreaction may vary from a few hours to as many I as 20 hours. I

I CoMPosnIoN OF MA TER Example 2 The same procedure is followed asin'Composition'of matter, Example'Lfe'xcept that'one ems ploys a,hydroxylatedintermediate product described under Completely acylatedproducts, Example 2, preceding, instead of in Example 1. 1

COMPOSITION or MATTER Example 3 The same procedure is followed as inComposition of matter, Example 1, except thatone employs a hydroxylatedintermediate product described under Completelyacylated products, Ex,-ample 3, preceding, instead of in Example 1. a CoMPosnroN or MATTEREram' The same procedure is followed as in Composition of matter,Example 1, except that one em-v ploys a, hydroxylated intermediateproduct described under Completely acylated products, Example 4,preceding, instead of Example 1.

CoMPosITIoN or MATTER Example 5 The same procedure is followed as inComposition of matter, Example 1, except that one em-v ploysa-hydroxylated intermediate product described, under Completely acylatedproducts, Example 5, preceding,:instead of in Example 1. a

COMPOSITION OF MATTER Example 6 H i The same procedure is followed. asin Composi tion of matter, Example 1, except that one employs ahydroxylated intermediate product de- Thesame procedu'reis followed asinComposition of matter,-.Examples ,1 to 7, preceding, ex-

ceptrthat instead of using glycol ester intermediateproducts of the kindexemplified by ,Glycol ester, intermediate products, Examples 1,2 and 3,-jpreceding, there are exemplified products :of

. thev kinddescribedin- Glycol esterv intermediate products-Examples 4to 7, preceding,f In such previous examples, which include the use ofricinoleicacid, "attention-is directed :to

thefact that excellent products of unusual value are obtainable bysubstituting oxyalkylated ricinoleic acid, particularly oxyethylatedricin- ,2

@leib ea/ m n oifi ne s id- The n wration of s uc h material iswelllznow'n, and preferablyinvolves the following procedure:

I Triricinolein in theform of castor oil-is treated of triricinloleiir On e 'half I of sodium ee n r sodium. r q 'q ea i edu catalyst. Atemperature ofY1-00-200 C. is employed. The reaction is conductedvarying from 100 lbs. to BOO-lbsgaugepressuie. The waterinsolubleoxyethyla'tedtriricinolein so obtain'e is saponified so as to yield awater-insoluble xyethylated ricinoleicfacid', or one which atthe most"isself emulsiiying.f1 1

' Reviewing what has "been 'said, it is obvious that a wide'range incarbon atom content e'x'istsin I regard "to the alcoholic bodiesemployed for re-' action with the glycol dihydrogenidiacid ester.

For instance, such alcoholic'body might contain two ethylene radicals,ft'woacetyl radicals, and one iic'inoleyl radical, totaling 26 carbonatoms. On the other hand, derivatives from apentamine 2 containing *3*ricinoleylradicalsfor example,

might readily contain approximately 60 or' IO carbon atoms, or even inexcessof 70 carbon are employed priorto reaction with the glycol esterare largely of the water-soluble type, but I atoms, providedthat insteadof acetic acid, one

used a low molal monocarboxy acid havinga.

larger number. of carbonatoms. i

- Itis to be'noted that ithissecondstepzisan esterification reaction;and the same procedure 5 is employed as suggested above in' thepreparation, of 5 the. intermediate, product. Needless .to say, anyparticular. method fmaylbe used to pro duce' the desired compounds ofthe kind indicated. In some instancesit may be desirable 55 to conductthe esterificati'on reaction in the presence of a non-volatile inertsol-vent. which simply acts as a diluent or'viscosity reducer.

ln thepreceding examples, attentiomhas been directed primarilyto themonomeric form, or, at least, to the form which thebifun'ctionalalcohol, i. e., a glycol, andthe polyfunctional acid,

usually a bifunctional compound, react'to give a chain type compound",in which the adjacent acid andgly'col nucleus oecur-a's a structuralunit. 65 For instance; in the monomeric form this may be indicated inthefollowing manner: acid ...gly'col....acid" If, however, one preparedan intermediate product employingt'heratio of three moles of ,7

with 3-12 moles of ethyleneoxide foreach more,

*6. j es-reset Similarly, three moles; of -the glycol and rear molesofthe acid might-tend tove a comma ti'on'which may be indicated'tl'i'us'acid. glycol acid glycol (acid glycol acid Another way of stating thematter isthat the composition maybe indicated 'in the following manner:I I 'roooncooi (021140 ym 1o2 noooncoo] er in which the characters havetheir previous fs'ignificance" and a: is a, relatively small wholenumber less than 10 andlprobablylle's'sthan5 I and in the monomericformx, of coinse, is l. The limil tations on the size of .ztare probablyinfluenced, 5 largely, by the fact that reaction leadingto'fiirthergrowth is dependent, upon random contact.

Some of 'the productsare s'e'l-f- -emiil'sifiable oils,

or self-emulsifiable-compounds, whereas, others give cloudy solutions orsols; and the most desirable type is characterized by giving a clearsolution in water, and usually in the presence of soluble calcium ormagnesium salts, and fre quently, in the presence of significant amountsof either acids or alkalies. l,

Water solubility'can be enhanced in a number of ways which have beensuggested by previous manufacturing directions, for instance:

(a) By using-amore highlypolynierized ethylene glycol; \II 1.

(b) By using a pol 'eric form "insteadofa monomeric form in regard tothe unit which form the chain between the two alcoholic nuclei;

(0), By using a polyba'sic carboxy acid of lower molecular weight,gforinstance; maleic acid instead of adipicacidyanda I r (d) By, using ,analcoholic reactant of lower molecular weight, or-one having morehydroxyl groups, or, possibly, having oneHor more ether groups. v I

Indeed, in many instances, the hydroxylated,

body may show sometendency towards water solubility or selfemulsification prior to reaction with a glycol ester. It is to be notedin this instance that the; hydroxyla ted' materials which in suchinstances wheretheyarefself emulsifiable, or show hydrophobeproperties'they are equally suitable. e

Actually, a reaction involving an alcohol and an acid (esterification)"may permit small amounts of either one :or both of the reactants,

depending upon, the predetermined proportion,

to remain in an unreacted state. In the actual preparation ofcompositions "of thefherein contemplated, any residual acidity can beremoved'by any, suitable base, for instance,-am-

monia, triethanolamine, or the like," especially in Y 1 dilute solution.*Naturally, precaution shouldbe takenQso that neutralization takes placewithout saponification or decomposition of the ester. :QIn some casesthere isnopbjection to the presence of the acidicgijoupI Irideed, i f atribasicv acid be employed insuchlamannera to leaveone free carboxylgroup, then it-Iis usually desirable to -,neutralize such group bymeansof a suitable f find uses as wetting, detergent, and levelingagents inthe laundry, textile, and dyeingindustryyas wetting a gents .anddetergents in :the; acid .washingof fruit, in the acid washingofbuildingstone and brick; as a wetting agent and spreader in theapplication of asphalt in road building and the like, as a constituentof soldering flux preparations; as a flotation reagent in the flotationseparation of various minerals; for flocculation and coagulation ofvariousaqueous suspensions containing negatively charged particles, such-as sewage, coal washing'waste water, and various trade wastes and thelike; as germicides, insec ticides, emulsifiers for cosmetics, sprayoils; wa-

ter-repellent textile finish, etc. These use are by no'means exhaustive.

However, the most .important phase of "the present invention, as far asindustrial application goes, is concerned with the use of the materialspreviously described as demulsifier for water in-oil emulsions, and morespecifically,

drilling mud contains added calcium-carbonate or the like to render themud'susceptible to reaction with hydrochloric-acid or the like, and thusexpedite its removal.

Chemical compounds of the kind herein descn'bed'are also'of value assurface tension depressants in the acidization of calcareous oilbearingstrata by means of strong mineral acid, such as hydrochloric acid.Similarly, some memhere are effective as surface tension depressants orwetting agents in the flooding of' exhausted oil-bearing strata. i i

As to using compoundsof the kind herein'described as flooding'agents'forrecoveringoil from subterranean strata, reference is made to theprocedure described in detail in U. S.'Patent' No. 2,226,119, datedDecember 24, 1940, to De Groote and Keiser. As to using compounds of thekind herein described as demulsifiers, or in particular as surfacetension depressants, in combination with mineral acid or acidization of:oil-bearing strata, reference is made to U. S. Patent No.

2,233,383, dated February 25, 1941, to De 'Groote and Keiser.

It will be apparent to those skilled in the art that residual carboxylacidity canbe eliminated by esterification with a low molal alcohol, forinstance, ethyl, methyl, or propyl alcohol, by conventional procedure,so as to give a substantially neutral product. The introduction of suchlow molal hydrophobe groups does not seriously affect the solubility,and in some instances, gives increased resistance, to soluble calciumand magnesium salts, for such property isof particular value. Usually,however, neutralization with a dilute solution of ammonia or the like isjust as practicable and less expensive.

In the hereto appended claims, it is intended lene glycol having atleast .7 and not more, than 17 ether linkages, and the alkylene radicalthereof containing at least 2 and not more than 6 carbon atoms; and (B)a ,polybasiccarboxy acid having 1 not more than 6 carbon atoms;and-theratio. of

, the esterifying reactants being Within the range of more than 1 andnot over 2 moles of the polybasic acid for each mole of the glycol; andsaid basic hydroxylated acylated polyamin'o compound free from etherlinkages being of the following formula:

in which n represents a small whole number varying from 2 to 10; a: is asmall whole number vary ing from 0 to 10, Z is a member of the classcon{ sisting of H, 'RCO, RCO, and D, in which RCO represents an acylradical derived'from a detergent-forming monocarboxy acid; R'CQ is'anacyl radical derived from a lower molecular Weight carboxy acid having6' carbon atoms or less; and D is a member of the class consisting ofalkyl, hydroxyalkl, aminoalkyl, and acyloxyalkylene, in which instancethe acyl group is a member of the class'consisting of RC0 and R'CO; andthe acylated polyamine is further characterized by the fact; that theremust be present a member of the class consisting of (a) acyloxyalkyleneradical,.

cluded are those which appear in the aforementioned U. S; Patent No.2,243,329, to' De Groote and Blair, dated May '27, 1941, that particularpatent'being concerned with a basic type acylated polyamine of thefollowing formula:

. Z Z in ,which n represents a small whole number varying from 2 to 10a: is a small wholenumbervarying from 1 to 10 Z is a member of the,class consisting of H300, RCO, and D, in whichRCO represents an acylradical derived from a higher molecular weight carboxy acid;RCOis-anacyl that the monomeric forms contemplate also the hydroxylatedacylated polya nino compound, free from ether linkages; the polybasiccompound being the esteriiicationproduct of: (A) a polyalkyradicalderived from a lower molecular weight carboxy acid having '6 carbonatoms orless; and

.hydroxyalkl, aminoalkyl, and acyloxyalkylene, in

whichinstance the acyl group is amember of the class consisting of RC0and R'CO; and the acylated-polyamine is further characterized by thefact that there must be present a member of the class consisting of -(a)acyloxyalkylene radicalin which the acyl group is RC0; and (1)) jointoccurrence of an amide radical in which the acyl groupis RC0 and ahydroxyalkyl radical.

The present invention is concerned with a water-soluble esterificationproduct, derived byreaction between onemole of a polybasiccompound andtwo moles of a basic hydroxylated acylated polyamino compound free fromether linkages; the polybasic compound being the este'rification productof (A) a polyalkylene glycol at least=2and notmore than 6 carbon atoms;and

', new" t'li') ,alpolybasicxcarboxy "acidhaving :not more I Q 1 than-6carbon atoms; :an di'the ratio :o fth'e esten- .fying reactants bein' gwithin the: range of "more 1 in which all characters have their previoussignificance, except that :12, instead of varying from' y 0 to 10,varies 'from 1 to 10. Y

ithanland not'over Zmcil'esof :tl'i etpolybasioacid lier eachqmoleoftthe glycol; and said basic by I zd roxylat'ed lacy-latedi .polyamino'compound free. f'rom etherll-inkages :beingpof thefol'lowingior- "iiiga'cidiis a higher m acid: having 18 carbon 1 :6. 'Theanylatedderivative, as definedin claim '-I,-:wherein' the' :c'ompound isneutral; the polyioarboxy acid is dicarboxm the jpolyal-kylene' gly-'toolv is a polyethylene :glycol, and the detergent- :iiorming acid is'an unsaturated higher fattyfacid 18-carbon atoms.

. -7. iihe :acylatedderivative}defined in claim 1, wherein the compoundis neutral; the-polycarboxy aLoid- -is dicarboxy; the polyalkyleneglycol is-a nonaethyl'eneyglycol, andct'h'edetergent-atomithe-lpreferred -xtypethere is present :at least f- -onebasic amino nitrogen atom.

Havingthus described our. invention, what we claim as new and desire tosecure by Letters Patentof the UnitedStatesisz. r

I 1. A water-solu'ble:acylatedderivative ofaba'sic 1hydroxylated-polyamine of the following formula:

in which 1i represents asmall whole number vary-' 5 ,ing from 2th 10; :0represents a small whole num- 1 "ber Varying "from 1 to T0; 'R'C'O isan, acyl radical ofi'a; lower molecular weightcarboxy acid having l "5carbon ai lon'is orless; R," is a member of the f 1 "class consisting.of hydrogen atoms, alykl radicals, 3 hydroxyalkyl radicals andacyloxyalky1ene'radi icals'in which the acyl'radical isRC'O'; thepolyamine is further characterized by the fact that i i there must bepresent a j consisting'of: (a) 'Acyloxyalkylene radical in which theacyl 5 *member of the class (b) .Joint.,.occu-rren'ce of anzamidoradicaliin which i 3 in all occurrences RCOJis. a detergent-iorming Qthe acyl group is RC0 and a radical; I

monocarboxy acyl radical having at least 8 and not more than 32 carbonatoms; the acyl group substituted for a reactive hydrogen atomoi sa-id 5*acylatedb'a'sic hydroxylated amine being the 'acyl 3 radicallofianacidic fractional ester, in which the 1 alcoholiradical is t'hat of apol-yalkylene-g'lycol having 52,1? least 7: and not more than- TI -etherl linkages; and the alkylene radical thereof can- 1' tainingiatz least'2 :and not more than-"6 carbon 1 'atoms, ;.'and the: acidxradical ofsai-d acidic frac- .tional festerzais .that ofaipolycarboxy acid havingnot more than. 6 carbon .atoms; and the ratioof theipolycarboxyacids-radicals .to-the glycol -radi- 1 cals in saidfractionalrester:beingiwithintherange j of "more than .1 andznot' over2' mole equivalents of the polycarboxy acid radical for each moleequivalent oftheyglycolradical. I

r g e acylated derivative as defined in claim j =1,wherein-the-compoundfis neutral;

3. The acylated' derivative as defined in claim v .1, wherein thecompound isneutralrand carboxy. vacid -is 'dicarboxyl.

the poly- 4. The acylated derivative, as defined in'claim 1, wherein thecompound isnelltra'l; the tpolyc'ar- 1 v .boxy acid is dicarboxypandtherpolyail ylenegly- 99 i a e h n 'p ,.5. .The .acylated denivative,.as'defined inclaim;

ing acid is an unsaturatedv ing l 8' carbon atoms.

8. Theacylat'ed derivative, as defined in'claim 1, wherein the compoundis neutral; the polycarbox-y acid is dicarboxy;-the pelyalkylene glycolv is a rionaethylene glycol, and the detergent-form: ving acid isricinoleic acid.

-9-."I he acylated derivative, asdefine'd inclaim 1, whereinthe compoundis neutral; the polycarboxyacid is dicarboxy; the polyalkylene glycolisanonaethylene glycol; the detergent-forming acid is rieinoleic acid,andrthe polyamino radical is a .dieth-ylenetriamine radical.

;10. Theacylated derivative, as 'definedin claim 1, wherein the compoundis-neutral; the polycarboxy-acid is d-icarboxy; the polyalkylene glycolis :a-nonaethylene glycol; the detergent-forming ,acidis ricinoleicacid, and the polyamino radical is'a triethylenetetramine radical.

1.1. ilheacylated derivative, as defined in claim .L,whereingthecompound is neutral; the polycarbox-y acid isdicarboxy; thepolyalkylene" glycol is a nonaethylene glycol; the detergent-formingacidwis ricinoleic acid, and the -.polyamino radical isa-triethylenepentamine radical; T

' (12. In the manufacture of .an acylated derive V tive, as defined-inclaim 1, the steps of:

( A)- Esterifying a polyalkylene glycol havingat v of abasichydrogeylated polyamino compound of the-following formula:

R" c o I R t i in whichn,represents asmall whole number varying .from 2to 10; 0: represents a small whole number varying from '1 to 1'0; R'COis an acyl radical of a lower molecular weightcar-boxy acid having 5carbon atoms or less; R a member o'f-"tlie class consisting of hydrogenatoms, alkyl radicals, "hydroxyalkyl radicals and acylox'yalky..leneiradicals which the vacyl"radi'c'al is RCO; the pol'yamine isfurther characterized b'y th'e' fact that there mustb'e present a memberof thecla'ss 7 consisting I of Ca')" 'acyloxyalkylen'e radical in whichthe-*acyl "group is "RC0: "and ('17) joint occurrence of-"anaimido'radicalin which the acyl groupis'RCO -and a-hydroxyalkyl"radical:in an occurrences RC0 is a detergent-forming monooar boxy 'aoyl radicalhaving atleast 8 and'not 1,; wherein the. compound is. neutral; thepolycar- 3 uboxy acid is dicarboxy; the ;polyalkylene. glycol l is -apolyethylene:glycohiandthe detergent form- .iii

atoms; I

m'ore tli'ani 52 ca'rbon higher fatty acid havencore;

